TW586332B - Polymeric fluorescent substance and polymer light-emitting device using the same - Google Patents

Abstract

Provided is a polymeric fluorescent substance comprising a copolymer which has a substituent containing a specific aromatic amine structure below in the side chain, wherein X1 is a divalent hydrocarbon group; Ar2 is an arylene group or the like; and Ar3 and Ar4 independently represent an aryl group or the like. The polymeric fluorescent substance is preferably used for a light-emitting layer of a polymer LED having high luminance and high light-emitting efficiency.

Description

586332

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs [Background of Invention] [Invention Category] The present invention relates to a polymerized fluorescent substance and a polymer light-emitting device using the polymerized fluorescent substance (hereinafter sometimes referred to as polymer LED) . [Related technical description] Unlike low-molecular-weight luminescent materials, polymeric luminescent materials (polymeric fluorescent substances) are soluble in solvents and can be used to form light-emitting layers in light-emitting devices by coating methods. Such polymeric fluorescent substances have been studied in many aspects . In recent years, polymerized fluorescent substances containing fluorene units have attracted attention. In order to improve the performance, copolymers containing one fluorene unit and other units have been studied. In other copolymers, it is disclosed that a copolymer containing an aromatic amine structure (hereinafter referred to as an aromatic amine unit) as other units is disclosed, for example, a polymerized fluorescent substance includes a copolymer including a fluorene unit and a Aromatic amine unit with a nitrogen atom in the main chain (WO 99/543 85). However, the aforementioned polymerized fluorescent substance containing a fluorene unit and an aromatic amine unit having a nitrogen atom in the main chain has its problems. When the polymerized fluorescent substance is used as a light emitting layer, its brightness and luminous efficiency are insufficient. The object of the present invention is to provide a polymerized fluorescent substance including a copolymer. The copolymer has a substituent containing a specific aromatic amine structure in a branched chain. When the polymerized fluorescent substance is used in a light-emitting layer, a high fluorescence can be achieved. Brightness and high luminous efficiency functions, and a polymer LED using the polymerized fluorescent substance. [Summary of the Invention] The present invention relates to a kind of polystyrene fluorescein which emits fluorescence in a solid state. It is a Chinese National Standard (CNS) A4 specification (210 X 297 public love) '' 1 313883 (Please read the back Note for this page, please fill in this page) ------- Order --------- line

586332 A7

The number of mouths is an average molecular weight of 103 to < a fluorescent substance, which contains ^ ^ aq: a repeating unit represented by formula ⑴ and-or a repeating unit represented by multiple formula 早, ΑΓι_ (1) Wherein AΓι represents an arylene group or a divalent heterocyclic compound group, and there are 1 to 4 substituents represented by the following formula (2), ~ ^ Χι ^^ \ αγ2-N

(2) wherein X1 is a divalent hydrocarbon group; Aq represents an aryl group or a divalent heterocyclic compound group; Aq represents an aryl group or a monovalent heterocyclic compound group; A. And A. May be linked to form a ring; Ah represents an aryl group or a monovalent heterocyclic compound group; Ars and Aq may be linked to each other to form a ring; k is 0 or 丨; 丨 represents an integer of 1 to 3, _Ar5_ (3) where Aq represents an aryl group or a divalent heterocyclic compound group represented by formula (4) or (5): (Please read the note on the back? Matters before filling out this page)

-------- Order --------- line

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

X2 represents a group selected from 0, S, SO, S02, N-R3, CR4R5, SiR6R :; 3 to 117 each independently represent a group selected from a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic compound group I and R2 each independently represent a group selected from the group consisting of alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, National Standard (CNS) A4 (210 X 297 mm) 2 313883 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 586332 A7 __ B7 V. Description of the Invention (3) Aryl, aryloxy, arylsilyl, arylamino, arylalkyl, arylalkyl, Aryl alkyl, aryl alkyl, aryl alkenyl, aryl alkenyl, aryl alkynyl, monovalent heterocyclic compound groups, and cyano groups; m and n are each independently 0 to 3 Integer; when m is 2 or more, multiple hearts may be the same or different; when η is 2 or more, multiple r2 may be the same or different, · R! To & may be connected to form a ring; When Ri to & is an alkyl group-containing group, the alkyl group may be interrupted by a heteroatom-containing group, (5) where R8 represents a group selected from alkyl and Alkyl, sulfanyl, sulfanyl, alkylamino, aryl, aryloxy, arylsilyl, arylamino, arylalkyl, arylalkyl, arylalkylsilyl , Arylalkylamino, arylalkenyl, arylalkynyl, monovalent heterocyclic compound groups, and cyano groups; j is an integer from 0 to 3; when j is 2 or more, more Each r8 may be the same or different. When Re is an alkyl chain-containing group, the alkyl bond may be broken by a heteroatom-containing group. In addition, the present invention relates to a polymer light-emitting device, including a pair of electrodes made of an anode and a cathode, at least one of which is transparent or translucent, and at least one light-emitting layer between the two electrodes, wherein the light-emitting layer includes the foregoing Aggregate fluorescent substances. [Detailed description of the invention] The polymerized fluorescent substance of the present invention emits fluorescence when in a solid state, and has a polystyrene-reduced number average molecular weight of 103 to 108. Polymer fluorescent materials contain fractions, using China National Standard (CNS) A4 specifications (210 X 297 mm) ------- 313883 (Please read the precautions on the back before filling this page)

^ «6332

V. Description of the invention (4 Do not repeat units represented by the above formulas (1) and (3). The total repeat unit represented by formulas (3) and (3) is based on the total repeat units as the reference material. It is the dome ratio or more.) The repeating director of formula 疋 ^, the total number of repeating units expressed by formula ⑴ and (3) as a reference is suitable to be above 0% Mohr㈣ to 5G% Mohr U. Better formula ⑴ and (3 The total number of repeating units represented by) is equal to or more than the molar ratio of all repeating units', and the repeating unit decrement represented by formula (i) is 0.1% of the total repeating units represented by formula (i) and (3). 50% by mole ratio or less. The repeating unit represented by the above formula (1) is an arylene group or a divalent heterocyclic compound group having from 1 to 4 substituents represented by the above formula (2). The above formula (3) The repeating unit represented by the formula (4) or (5) is a bivalent compound. The repeating unit represented by the formula (4) is an extended f group bridged between two benzene rings, which may have one substituent. The repeating unit represented by the above formula (5) is a phenylene group which may have one substituent. As for the specific example of the repeating unit represented by the formula (5), the formula (6) is heavy. Unit (Please read the notes and then fill in the back of this page) fluorenyl _2,7_ group, set --------- line

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Among them, u and R12 each independently represent a group selected from a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic compound group; r9 and rig each independently represent a self-alkyl group, an alkoxy group, a thio group, Carbonyl, carbonyl, aryl, aryl, arylsilyl, arylamino, arylalkyl, arylalkane Zhongguan Standard (CNS) A4 (210 X 297 mm) " ' 4 313883 586332 V. Description of the invention (5-oxy group, aryl radical, aryl radical, aryl radical amine, aryl dilute radical, aryl alkynyl, monovalent heterocyclic compound radical, and radical radical 圏; Μ] are each independently an integer of 0 to 3. When h is 2 or more, multiple & may be the same or different; when i is 2 or more, multiple A. may be the same or different 'Ά can be linked to form a ring; when r12 is a group containing a sulphur group, the base chain can be interrupted by a heteroatom-containing group. Taryl is an aromatic hydrocarbon in which two hydrogen atoms are removed Atomic group. Aromatic hydrocarbon is a cigarette used as a matrix of aromatic compounds, which contains a benzene ring. Aromatic hydrocarbons also include a condensed ring, and: one or two The above independent benzene ring or condensed ring is bonded to the aromatic hydrocarbon via a direct bond, ethylene and other groups. The aryl group usually contains 6 to 60 carbon atoms, including, for example, phenylene, phenylene, and phenylene. Triphenyl, oxalyl, naphthyl, anthracyl diyl, etc. The number of carbon atoms of the substituent is not calculated as the number of carbon atoms of the phenyl group. A divalent heterocyclic compound group means that two fluorene atoms are removed Heterocyclic compound atom group. Heterocyclic compound represents a cyclic structure of the Intellectual Property Bureau of the Ministry of Organic Economics, and it is printed by a cooperative, which enables at least one heteroatom such as oxygen, sulfur, nitrogen, saucer, etc. It is contained in a cyclic structure as an element other than a carbon atom. The divalent heterocyclic compound group usually has 4 to 60 carbon atoms, including, for example, furandiyl, thienyl, fluorenediyl, pyridyldiyl, pyrimidinediyl, Quinoline mono, quinoline diyl, etc. Here the number of carbon atoms of the substituent is not calculated as the number of carbon atoms of the divalent heterocyclic compound group.… As for the example of AΓι, including having two or more as above through combination Divalent heterocycle The group of the structure obtained from the compound group. "X 297 mm" This standard (CNS) A4 specification (210: 5 313883 586332 A7 _____B7 V. Description of the invention (6) Among them, phenylene, phenylene, naphthalene Diyl, anthracene diyl, pyridoxyl, thienyl, quinoline diyl, and quinoxaline diyl are more preferred.

Aq contains 1 to 4 and preferably 1 to 2 substituents represented by the above formula (2). AΓι may have a substituent other than the substituent represented by the above formula (2). As for the substituent other than the substituent represented by the above formula (2), examples include alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylsilyl, Arylamino, arylalkyl, arylalkyl, arylalkyl, arylalkylamino, arylalkenyl, arylalkynyl, monovalent heterocyclic compound, cyano, etc. . As for the specific example, it is the same as the latter and & Xi in the above formula (2) represents a divalent hydrocarbon group. A divalent hydrocarbon group is a hydrocarbon atom group that usually contains about i to 20 carbon atoms with two hydrogen atoms removed. Specific examples are alkylene, alkenyl, alkynyl and polymethenyl. More specific examples are, for example, methyl, ethyl, propyl, vinyl, ethynyl, substituted vinyl, propyl, butyl, and the like. Among them, vinylidene and substituted vinylidene are more preferred. As the substituted vinylidene group, for example, a vinylidene group having a methyl group, an ethyl group, a phenyl group or a cyano group as a substituent. Ars of the above formula (2) is an arylene group or a divalent heterocyclic compound group. The definitions of the arylene group and the divalent heterocyclic compound group are the same as those of AΓι, and the specific and preferred examples thereof are the same as described above for AΓι. (Please read the Zhuyin on the back? Matters before filling out this page) I ------ ^ --------- line

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. In the above formula (2), Ars and Aq are each independently an aryl group or a monovalent heterocyclic compound group.

6 313883 586332 A7 B7 V. Description of the invention (7 Aryl groups usually contain 6 to 60 carbon atoms, such as phenyl, biphenyl, bitriphenyl, fluorenyl, naphthyl, anthracenyl, and have a substitution A monovalent heterocyclic compound group usually has 4 to 60 carbon atoms, including, for example, pyridyl, pyrimidinyl, furyl, thienyl, quinolinyl, sultinoyl, and its substituents. Among them, phenyl, naphthyl, anthryl, pyridyl, thienyl, quinolinyl, quinolinyl, and groups having one substituent are more preferable. When A ^ and Aq have one substituent The 'substituent' includes, for example, alkyl, alkyl, thio, alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylamino, arylalkyl, aryl Alkyloxy, arylalkyl, arylalkylamino, arylalkenyl, arylalkynyl, monovalent heterocyclic compound, and cyano.

Ars and Ars are connected to each other by a single bond or a divalent hydrocarbon group. Will A. The divalent hydrocarbon group to which Ars is bonded to each other usually contains about 1 to 20 carbon atoms. In particular, it is an alkylene group, an alkylene group, an alkylene group, and a polymethenyl group. Specific examples are methyl, ethyl, propyl, vinyl, ethynyl and the like. Among them, single bonds, methyl groups and vinyl groups are preferred. As for the group having a structural formula in which Ar2 and Ar3 are connected to each other by a single bond or a divalent hydrocarbon group, for example, a carbazolyl group or a substituted carbazolyl group. As for the substituted carbazolyl substituents, for example, alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylsilyl, arylamino, aryl Arylalkyl, arylalkoxy, arylalkylsilyl, arylalkylamino, arylalkenyl, arylalkynyl, monovalent heterocyclic compound, and cyano. (Please read the Zhuyin on the back? Matters before filling out this page) Order --------- line

Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, National Standard (CNS) A4 Specification (210 X 297 mm) 7 313883 586332 A7 B7 V. Description of Invention (8) Αγ3 and Ar4 can be the same as Αγ2 and Αγ3 above Ways are connected to each other. The example represented by formula (2) is shown below. Further exemplifying a group having a substituent having one or more substituents on its benzene ring is, for example, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, Aryl alkyl, aryl amino, aryl alkyl, aryl alkyl, aryl alkyl, aryl alkyl, aryl diaryl, aryl alkynyl, Heterocyclic compound groups and cyano groups. Examples of the group having a substituent such as an alkyl group, an aryl group, and an arylalkyl group on the vinyl group are also exemplified. (Please read the notes on the back before filling out this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm): 3 " 691 ------- order ---------

313883 586332 A7 B7 V. Description of the invention (9) Among which the following groups are preferred

-CH ^ CI

—CH = CH · P2H5

(Please read the notes on the back before filling this page)

In the repeating unit indicated by the printed formula of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the 14 * phenyl group is preferably 14 • phenyl, which is more preferably a substituent having an n-type ⑺ table *. Among the substituents represented by 2), 1,4-phenylene having two substituents at 2,5 is more preferred. The repeating unit represented by the above formula (3) is a divalent compound group represented by the formula (4), (5) or (6). The heart of formula ⑷ and R2, the heart of formula (5) and the heart of formula (6) and &. Each independently represents a member selected from the group consisting of alkyl, alkoxy, alkylthio, alkylalkyl, alkylamino, aryl, aryloxy, arylsilyl, arylamino, arylalkyl, An arylalkoxy group, an arylalkylsilyl group, an arylalkylamino group, an aryl dilute group, an aryl alkynyl group, a monovalent heterocyclic compound group, and a cyano group. The heart of the repeating unit represented by the above formula (4) and r2, the repeating unit represented by the above formula (5) and the repeating unit represented by the above formula (6) are 9 and R10 when it is a substituent other than a cyano group The description is as follows. The entertainment base can be any one of straight chain, branch or ring, usually containing about 1 to China National Standard (CNS) A4 specification (X 297 mm) 9 313883 — — — — — — — 11111111

V. Description of the invention (ίο The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints 20 carbon atoms' and special examples include methyl, ethyl, propyl, isopropyl, isobutyl, second butyl, pentyl, Isopentylhexyl, cyclohexyl, heptyloctyl, 2-ethylhexyl, nonyl, decyl, 37 dimethyloctyl, lauryl, etc .; preferably pentyl, isopentyl, hexyl, octyl , 2-ethylhexyl, decyl, and 3,7-dimethyloctyl. ^ Alkoxy may be any of linear, branched, or cyclic, and the number of carbon atoms is usually 1 to 20, and special examples include Methoxy, ethoxy, propoxy, isopropoxy, butanyl, isobutoxy, tertiary butoxy, pentoxy, isopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy Octyl, octyloxy, ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, etc .; preferably pentyloxy, isopentyloxy, hexyloxy Octyl, octyloxy, 2-ethylhexyloxy, decyloxy, and 3,7-dimethyloctyloxy. The thiothio group can be any of linear, branched, or cyclic, and usually contains about 1 Up to 20 carbon atoms, with special examples including methylthio, Thio, propylthio, isopropylthio, butylthio, isobutylthio, tertiary butylthio, pentylthio, isopentylthio, hexylthio, cyclohexylthio, heptylthio, octyl Thio, 2-ethylhexylthio, nonanthio, decylthio, 3,7-dimethyloctylthio, laurylthio, etc .; preferably pentylthio, isopentylthio, hexylthio , Octylthio, 2-ethylhexylthio, decylthio, and 3,7-dimethyloctylthio. The alkyl radical may be any of straight chain, branched, or cyclic, usually containing about 1 to 60 carbon atoms, and specific examples include methylsilyl, ethylsilyl, propylsilyl, isopropylsilyl, butylsilyl, isobutylsilyl, third butylsilyl, pentyl Silyl group, isopentyl silyl group, hexyl silyl group, cyclohexyl silyl group, heptyl silyl group, octyl silyl group '2- (Please read the note on the back? Matters before filling out this page)

— II --— —Order----- I 11 I

This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) G32696 313883 586332 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (11) Ethylhexylsilyl, nonylsilane Base, decylsilyl, 3,7-dimethyloctylsilyl, laurylsilyl, trimethylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldiyl Methylsilyl, butyldimethylsilyl, tert-butyldimethylsilyl, pentyldimethylsilyl, isopentyldimethylsilyl, hexyldimethyl Silyl, heptyldimethylsulfanyl, octyldimethylsulfanyl, 2-ethylhexyldimethylsulfanyl, nonyldimethylsilyl, decyldimethylsilyl, 3 , 7-dimethyloctyldimethylsilyl, lauryldimethylsilyl, etc .; preferably pentylsilyl, isopentylsilyl, hexylsilyl, octylsilyl, 2-ethyl Hexylsilyl, decylsilyl, 3,7-dimethyloctylsilyl, pentyldimethylsilyl, isopentyldimethylsilyl, hexyl Methyl silicon alkyl, silicon alkyl dimethyl octyl, 2-ethylhexyl dimethyl silicone, decyl dimethyl silicone and alkyl-dimethyl-3,7-dimethyloctyl silicon group. The amine group may be any of linear, branched, or cyclic, it may be a amine group or a dialkylamine group and usually contains about 1 to 40 carbon atoms, and specific examples include methylamine group, dimethylamine group , Ethylamino, diethylamino, propylamino, isopropylamine, butylamine, isobutylamine, tertiary butylamine, pentylamine, isoamylamine, hexylamine, cyclohexylamine, Heptylamino, octylamino, 2-ethylhexylamino, nonamino, decylamino, 3,7-dimethyloctylamino, laurylamino, etc .; preferably amylamine, isoamylamine Base, hexylamino, octylamino, 2-ethylhexylamino, decylamino, and 3,7-dimethyloctylamino. Aryl groups usually contain about 6 to 60 carbon atoms, and specific examples include phenyl, Ci to C12 alkyloxyphenyl ((^ to C12 represent 1 to 12 carbon atoms, the same applies hereinafter), 6 to C12 alkyl Phenyl, 1-naphthyl, 2-naphthyl, etc .; preferably Cl (please read the notes on the back before filling this page)

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This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) C3C697 11 313883 586332 A7 B7 5. Description of the invention (12) to C12 alkoxyphenyl and q to c12 alkylphenyl. Aryloxy usually contains about 6 to 60 carbon atoms and is particularly phenoxy, (^ to C12 alkyl), (^ to C12 alkylphenoxy, 1-naphthyloxy, 2-naphthyloxy Preferred are phenoxy, C! To C12 alkoxyphenoxy, and C12 alkylphenoxy. Arylsilyl groups usually contain about 6 to 60 carbon atoms, such as phenylsilyl, C! To C12 alkoxyphenylsilyl, q to C12 alkylphenylsilyl, 1-naphthylsilyl, 2-naphthylsilyl, dimethylphenylsilyl, etc. Q to C12 alkoxyphenylsilane And q to C12 alkylphenylsilyl groups are preferred. Arylamino groups typically contain about 6 to 60 carbon atoms, with specific examples including phenylamino, diphenylamino, and G to C12 alkoxyphenyl groups. Amino group, bis ((^ to C12 alkoxyphenyl) amino group, bis (Ci to C12 alkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, etc .; preferably G to C12 alkoxyphenylamino and bis (Ci to C12 alkylphenyl) amino. Arylalkyl usually contains about 7 to 60 carbon atoms. Particularly examples are phenyl to C12 alkyl, q to C12 alkoxy Phenyl-Ci to C12 alkyl'q to C12 alkyl, phenyl-Ci to C12 alkyl, 1-naphthyl-(^ to C12 alkyl Alkyl, 2-naphthyl-Ci to C12 alkyl, etc .; q to C12 alkoxyphenyl to (: 12 alkyl, and Ci to C12 alkylphenyl-Cl to c12 alkyl are preferred. Group usually contains about 7 to 60 carbon atoms, especially phenyl_q to C12 alkylfluorenyl, C! To C12 alkoxyphenyl-Ci to C12 alkoxy, Cl to C12 alkylphenyl-Cl to C12 Alkoxy, 1-naphthyl-(^ to c12 alkoxy, 2-naphthyl_Ci to C12 alkoxy, etc .; Ci to C12 alkoxyphenyl_Ci This paper size applies to Chinese National Standards (CNS) A4 size (210 X 297 mm) (Please read the notes on the back before filling this page) Order --------- line

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 〇98 12 313883 586332 A7 ______B7 V. Description of the invention (U) to C12 alkoxy and < ^ to C12 alkylphenyl < 1 to Cu . Please read the notes on & before writing this page. Arylsilyl groups usually contain about 7 to 60 carbon atoms. Specifically, for example, phenyl-Cl to C12 alkylsilyl, Ci to C12 alkoxyphenyl-Cl to C12 alkylsilyl, 6 to c12 alkylphenyl-d to c12 alkyl crushed, 1-naphthalene -Cl to C12 alkylsilyl, 2-naphthyl-Ci to C12 alkylsilyl, phenyl-Ci to (12 alkyldimethylsilyl, etc .; Ci to c12 alkoxyphenyl-Cl To C12 alkylsilyl and Ci to c12 alkylphenyl to C 12 alkyl are preferred. Arylalkylamino groups contain about 7 to 60 carbon atoms. Particularly, for example, phenyl-q to c12 alkyl Amine, q to C12 alkoxyphenyl-Ci to C12 alkylamine, Ci to C12 alkylphenyl-Cl to C12 alkylamino, bis (Ci to <: 12 alkoxyphenyl-q to C12 alkyl Group) amino group, bis (Cl to C12 alkylphenyl-Ci to c12 alkyl) amino group, 1-naphthyl-(^ to C12 alkyl group, 2-naphthyl-(^ to C12 alkyl group) Etc .; Ci to C12 alkylphenyl-Cl to c12 alkylamino and di (q to c12 alkylphenyl-Ci to C12 alkyl) amino group are preferred. A monovalent heterocyclic compound group means a heterocyclic The compound removes one remaining atomic group, carbon atom, printed from the rubidium atom of the Intellectual Property Bureau of the Ministry of Economic Affairs. It is usually about 4 to 60, preferably 4 to 20. The number of carbon atoms of the heterocyclic compound group does not include the number of carbon atoms of the substituent. Here the term heterocyclic compound includes organic compounds having a cyclic structure in which The constituent elements include not only carbon atoms, but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, etc., which are also contained in the ring. Particularly, for example, thienyl, q to C " Benzyl, ^ to ... thiol, thiol, etc., and preferably thienyl, Ci to C12 alkyl thienyl, pyridine basic ^^^ 9 Chinese National Standard (CNS) A4 specification (210 X 297 public love ) ------ 13 313883 586332 A7 B7 V. Description of the invention (14 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and C1 to C12 alkylpyridyl. The repeating unit represented by the above formula (4) is from 3 to the heart And Ru and ri2 of the repeating unit represented by the above formula (6) each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic compound group. Rs to R? Of X2 and Zhixin 2 of formula (6) is described below when it is a substituent other than a hydrogen atom. Any of linear, branched or cyclic, usually containing about 1 to 20 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, Pentyl, isopentyl, hexyl, cyclohexyl, heptyl, octyl, 2.ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, etc .; preferably pentyl, Isoamyl, hexyl, octyl, 2-ethylhexyl, decyl and 3,7-dimethyloctyl. Aryl groups usually contain about 6 to 60 carbon atoms, and specific examples include phenyl, ^^ to Cu oxyphenyl ((^ to C1S represents 1 to 12 carbon atoms, the same applies hereinafter), (^ to Cls Phenylphenyl, 1-naphthyl, 2-naphthyl, etc .; preferably q to C1: 2 alkoxyphenyl and q to C12 alkylphenyl. The heterocyclic compound group usually contains about 4 to 60 carbon atoms In particular, for example, thienyl, q to (^ 2 alkylthienyl, pyrrolyl, furyl, 11 to fluorenyl, ^ to Cu alkyl, π to fluorenyl, etc.); and preferably thienyl, ^ to Cls Alkyl thienyl, pyridyl, and c! To C12 alkylpyridyl. In the repeating unit represented by the above formula (4), each of melon and η is independently an integer of 0 to 3. When m is 2 or more Multiple Ri may be the same or different. When η is 2 or more, multiple Ri may be the same or different. Any two of & to I may be connected to form a ring. In addition, when & to ^ Order for C32700 14 313883 (Please read the notes on the back before filling in this page)

586332 A7

5. Description of the invention (15 In the case of a group containing an alkyl chain, the alkyl chain may be interrupted by a heteroatom-containing group. In the repeating unit represented by the above formula (5), j is an integer of 1 to 4. When When j is 2 or more, multiple hs may be the same or different. When j is 2 or more, any two r8 may be connected to form a ring. In addition, when r8 is a group containing an alkyl chain, The alkyl chain may be interrupted by a heteroatom-containing group. In the repeating unit represented by the above formula (6), h and i are each independently an integer of 0 to 3. When h is 2 or more, multiple r9 may be the same or different. When i is 2 or more, multiple R1 () may be the same or different. Any two of r9 to Ri2 may be connected to form a ring. In addition, when R9 to R12 are contained In the case of an alkyl chain group, the alkyl chain may be interrupted by a heteroatom-containing group. Here, the heteroatom includes, for example, an oxygen atom, a sulfur atom, a nitrogen atom, and the like. A heteroatom-containing group includes, for example, the following groups (Please read the notes on the back before filling out this page) Order --------- Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs ο I RIB I-RIN Fresh

R 丨 S4—R one 〇 Ο Ο ο II II Μ Η II -C 10- C- -N-C- -q-N- where R represents an argon atom, a carbon atom containing 1 to 20 carbon atoms, Aromatic groups containing 6 to 60 carbon atoms and heterocyclic compound groups containing 4 to 60 carbon atoms 0 This paper size applies to China National Standard (CNS) A4 (210 x 297 mm) C32701 15 313883

586332 A7 ---------- B7 _. V. Description of the invention (16) '' -1 The alkyl group-containing substituent may be any of linear, branched and cyclic groups or a combination thereof, As for the non-linear group, for example, includes isopentyl, 2ethylhexyl, 3,7-dimethyloctyl, cyclohexyl, ... to A: alkylcyclohexyl and the like. In order to improve the solubility of the polymerized fluorescent substance ^ solvent, at least one of the substituents of the above formula ⑴ preferably contains a cyclic or branched alkyl chain. | In order to obtain a strong fluorescent substance, it is preferable that the repeating unit shape including a substituent | The symmetry of the formula is extremely low. In addition, be aware that when Ru is an aryl or heterocyclic compound group as part of the | structure, it may contain one or more additional substituents. Because the light-emitting properties and lifetime of the device may deteriorate when the polymerizable group remains as the end group of the polymerized fluorescent substance, the end group can be protected by a stabilizing group. It is preferable to use a conjugate structure having a conjugate bond continuous to the main chain, for example, a structure connected to an aryl group or a heterocyclic compound group through vinylidene. Specifically, for example, the substituent represented by Chemical Formula 10 is described in JP-Λ No. 9_45478 and the like. The synthesis method of polymerized fluorescent materials printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economics includes a polymerization method of alder coupling reaction with corresponding monomers, a polymerization method of Lignian reaction, a polymerization method using a nickel (〇) catalyst, A polymerization method using an oxidizing agent such as Feci3, a method by electrochemical oxidation polymerization, and a method by decomposing an intermediate polymer having an appropriate leaving group. Among them, in view of the ease of reaction control, a polymerization method using a Suzuki coupling reaction, a method using a Galia reaction, and a polymerization method using a nickel (0) catalyst are preferred. This polymeric fluorescent substance may contain repeating units other than the repeating units of formulas (1) and (3), as long as the light-emitting properties and charge transport properties are not deteriorated. This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 public meal) C32702 16 313883 586332 A7 V. Description of invention () Yes. Units of formula ⑴ and (3) repeating units or units other than formula ⑴ and (3) of repeating units may be connected through non-car combination units, or such non-combination units are also included in the repeat unit. As for the linking structure ', for example, as shown in the following chemical formula, a combination of the following chemical formula and vinylene, a combination of two or more of the following chemical formula, and the like are shown. Here R is selected from the same substituents as previously described, and M represents an nicotinyl group containing 6 to 60 carbon atoms.

-I? I? -6 — 一 Si— ~ c—

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This polymeric fluorescent substance can also be a random, block or graft copolymer, or a polymer with an intermediate structure, such as a random copolymer with blocking properties. From the standpoint of obtaining polymer fluorescent materials with high fluorescent quantum yield, it is better that the repeating regularity is lower, for example, random copolymers are better than alternating copolymers. In order to obtain an alternating copolymer, it is necessary to use monomers each having two kinds of reactive groups for polymerization. In this regard, the random copolymer can be obtained by feeding a plurality of monomers having one reactive group in a predetermined ratio, and the preparation is easy. Further 'random copolymers with blocking properties and non-uniformly sized block groups. W national standard (CNS) A4 specifications ⑵Q χ tear meals C32703 17 313883 (Please read the precautions on the back before filling (This page)

586332 5. Description of the invention (18% of block copolymers or graft copolymers are better than completely random copolymers. L package = polymer with branches and 3 or more end groups. This = also includes Regularly grown dendrimers and knots containing random branches are used as polymeric fluorescent substances, which are suitable for use in solid-state materials. The reason is that this substance uses light emission from thin films. As a polymeric fluorescent substance Good solvents include, for example, chloroform, digas methane, monogas ethane, tetrahydrofluorene, toluene, xylene, trimethylbenzene, naphthalene, decahydronaphthalene, n-butylbenzene, etc. Polymeric chelating substances are usually treated with The amount is based on the structural formula 3 of the polymerized fluorescent substance. The polymerized glory f has a number average molecular weight in terms of polystyrene = 10 to 108, and the degree of polymerization is also changed according to the repeating structure and its proportion. In general, the total amount of repeating structure is preferably 20000, more preferably 30 to 10,000, and particularly preferably 50 to 5000. When these polymerized materials are used as the light emitting materials of the polymer, the member of the Intellectual Property Bureau of the Ministry of Economic AffairsPrinted by the consumer cooperatives ~ Its, ^: the light properties affect, so it is preferred that the monomers be purified by methods such as distillation, sublimation purification, recrystallization, etc. before polymerization; in addition, it is preferred to carry out purification treatments such as reprecipitation purification, Chromatographic separation, etc. The polymerized fluorescent substance of the present invention can be used not only as a luminescent material, but also as an organic semiconductor material, an optical material, or as a rabbit conductive material by doping. 卞 The method for producing a polymerized fluorescent substance of the present invention The description is as follows. Method C327〇4 Coffee 3 586332 A7 B7

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586332 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 20 A7 B7 V. Description of the invention (20) Compounds with multiple reactive substituents as monomers, if necessary, can be dissolved in organic solvents, for example, in Organic solvents have a melting point or above to a boiling point or below for reaction using a base or a suitable catalyst. For example, known methods can be described in "Organic Reactions" Issue 14, pages 27 to 49, John Wiley & Sons, 1965; Organic Reactions, Issue 27, pp. 345 to 390, John Wiley & Sons, 1982; Organic Synthesis, Collection VI, pp. 407 to 411, John Willi & Sons, 1988; Synthesis of Chemistry, Issue 95, 2457 Page (1995); Journal of Organometallic Chemistry, No. 576, 147 pages (1999 Journal of Practical Chemistry, 336, 247 pages, 0994); Macromolecular Chemistry, Macromolecular Symposium, No. 12, page 229 (1987), etc. The organic solvents that are preferably used are fully deoxidized. The reaction is performed under an inert atmosphere. Usually, the reaction is to suppress side reactions, but the treatment is different depending on the compound used and the reaction. Dehydration treatment is performed in a similar manner (but not suitable for reaction with a two-phase system of water such as a Suzuki coupling reaction). For the reaction, a test or a suitable catalyst can be appropriately added. The catalyst can be selected and used according to the reaction used. A better test or catalyst can be used. It is fully dissolved in the solvent used for the reaction. As for the method of mixing the test or catalyst, for example, there is a method of slowly adding an alkali or catalyst solution while stirring under an inert atmosphere such as argon and nitrogen, or slowly adding the reaction solution to the test or Method of catalyst solution. Especially about the reaction conditions' Take Witti reaction, Horner reaction, Novenitz reaction as examples, using monomer functional group as the reference, 1 equivalent or more, preferably 1 The reaction is carried out to 3 equivalents of base. There are no special restrictions on the base. For example, metal alkanoates such as potassium tert-butoxide and tertiary butyl paper can be used in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm). ) 313883 Γ, ^ 27ηπ (Please read the precautions on the back before filling this page)

586332 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention () Sodium ethoxide, sodium formate, etc., such as sodium hydride, and ammonium amines, such as amina. As the solvent, N, N dimethylformamide, tetrazolium, Ershuya, toluene and the like can be used. The reaction can be carried out at a reaction temperature usually from room temperature to about ⑽. The reaction time is, for example, 5 minutes to 40 hours. It is permissible to use a time sufficient for the polymerization reaction because the reaction does not require a long period of time after completion of the reaction. The reaction time is preferably 10 minutes to 24 hours. The reaction degree is preferably appropriately selected from the range of about 0.01% by weight to the highest solution concentration, because the reaction efficiency is not good when the concentration is too low, or the control of the reaction is difficult when the concentration is too high, usually the concentration is 0.001%. To the range of 20%. When the Heck reaction is used, the single system is carried out in the presence of a catalyst such as triethylamine. The reaction is carried out using a solvent having a relatively high boiling point, such as n, n-dimethylformamide, N-methyl Π, etc., at a reaction temperature of about ⑼ to 160 £ 1 (: i to 1000 hours). Reaction time. When Tian performed the Lingmu coupling reaction, for example, [[(triphenylphosphine)]], palladium acetate, etc. were used as catalysts, and inorganic bases such as potassium carbonate, sodium carbonate, and barium hydroxide were used as organic compounds. B Amines and inorganic salts such as gasification must preferably be reacted by adding i equivalents, preferably 1 to 10 equivalents, based on the monomers. It is also allowed to use inorganic salts to aqueous solutions and react in a two-phase system. As for The solvent is, for example, N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran, etc. Depending on the solvent, a temperature of 50 to 160 ° F is preferably used. It is also allowed to increase the temperature close to the solvent The boiling point of rhenium induces reflux. The reaction time is about 1 to 200 hours. When performing the Glia reaction, for example, an exemplary method is a solvent in which a halide and a metal are ether-based, such as tetramethylenefuran, ethyl, and dimethyl ether. The paper size has passed the Chinese National Standard (cns) a4 specification (210 X 297 mm) ". C32707 21 313883 (Please read the note on the back? Matters before filling out this page) ------- Order ----- I --- line

22 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 刈 6332 V. Description of the invention (Recommended to prepare Glia reagent, which is combined with a separately prepared monomer solution, adding nickel or palladium catalyst, and pay attention to excessive reactions , And then the reaction temperature is increased to reflux and the reaction is performed. Based on the monomer, the amount of Glia is equivalent, preferably ... 5 equivalents, more preferably ^ 12 Although it is left. It is also undergoing polymerization other than the foregoing In the method, the reaction can be performed by a known method. Next, the polymer LED of the present invention will be described. Regarding the structure of the polymer LED of the present invention, a light emitting layer exists between the anode and the cathode, and at least one of the electrodes is transparent or translucent. The polymerized fluorescent substance of the present invention is contained in the light-emitting layer. As for the polymer LED of the present invention, it is worth mentioning that the polymer LED has an electron-transporting layer disposed between the cathode and the light-emitting layer, and a hole-transporting layer disposed between the anode and the anode. Polymer led between light emitting layers, polymer having an electron transport layer disposed between a cathode and a light emitting layer, and a polymer having a hole transport layer disposed between an anode and a light emitting layer For example, the following structural formulae 4 to d) are specifically illustrated. a) Anode / Light-emitting layer / Cathode b) Anode / hole-transport layer / Light-emitting layer / Cathode c) Anode / Light-emitting layer / Electron-transport layer / Cathode d) Anode / Hole-transport layer / Light-emitting layer / Electron-transport layer / Cathode (Where / represents the adjacent layer. The same applies hereinafter) Here, the light-emitting layer is a layer having a light-emitting function, the hole transmission dance is a layer having a hole-transmitting function, and the electron-transport layer is a layer having a function of transmitting electrons. Sword month b layer. Here the electron transport layer and hole transport layer are collectively referred to as the charge transfer wheel layer. The paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) G32708 (Please read the precautions on the back before filling this page)

313883 22 586332 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (23 The light-emitting layer, the hole transmission layer and the electron transmission layer can also be used independently for two or more layers. Among the transport layers, a charge transport layer having an improved charge injection efficiency from electrons and a function of reducing the driving voltage of the device is sometimes referred to as a charge injection layer (hole injection layer, electron injection layer). In order to improve adhesion to the electrode As well as improving the charge injection from the electrode, the aforementioned charge injection layer or insulation layer with a thickness of 2 nm or less is also provided adjacent to the electrode. In addition, in order to strengthen the interface adhesion and prevent mixing, a thin buffer layer can also be inserted into the charge transport layer. And light-emitting layer interface. The order and number of layers and the thickness of each layer can be appropriately adjusted while taking into account the device's luminous efficiency and fate. The present invention 'provides a polymer LED with a charge injection layer (electron injection layer, hole injection layer) , Enumerate polymer LEDs with a charge injection layer placed adjacent to the cathode, and A polymer layer disposed on the anode of the LED. Such as in particular illustrated structure e) to P). e) Anode / charge injection layer / light emitting layer / cathode / anode / light emitting layer / charge injection layer / cathode g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode h) Anode / charge injection layer / hole transport Layer / light-emitting layer / cathode I) Anode / hole transport layer / light-emitting layer / charge injection layer / cathode J) Anode / charge injection layer / hole transport layer / light-emitting layer / charge injection cathode Mid-year: National Standard ( cns) A4 (Please read the notes on the back before filling this page) —p ----- Order --------- u

23 313883 of 332

V. Description of the invention (cathode cathode cathode) anode / charge injection layer / light emitting layer / electron transfer layer / cathode l) anode / light emitting layer / electron transport layer / charge injection layer / cathode m) anode / charge injection layer / luminescence Layer / electron transport layer / charge injection layer / η) anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / 〇) anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs P) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode As for the special case of charge injection layer, such as the layer containing conductive polymer; set A layer between the anode and the hole transport layer and containing a material having a free potential between the free potential of the anode material and the free potential of the hole transport material contained in the hole transport layer; disposed between the cathode and the electron transport layer and A layer containing the following material: This material has an electron affinity between the electron affinity of the cathode material and the electron affinity of the electron transport material contained in the electron transport layer. When the aforementioned charge injection layer is a layer containing a conductive polymer, the conductivity of the conductive polymer is preferably 10-5 S / Crn or more to 103 S / cm or less; it is better to reduce the leakage current between the light-emitting pixels. It is 10-5 S / cm or more to 10 S / cm or less and preferably 10-5 s / cm or more to 100s / cm or less. Generally, in order to provide a conductive polymer with a conductivity of 10-5 S / cm or more to 103 S / cm or less, a suitable amount of ions is doped into the conductive polymer. The general category of ion doping, the anion is used for hole transport layer and cation L national standard (CNS) A4 as a view--24 313883 (Please read the precautions on the back before filling this page) ------- -^ --------- ^

View 332

V. Description of the invention (25 The printed ion system of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is used for the electron transport layer. Wang; 1¾ carved in, for example, polyanion anion, alkylbenzene sulfonic acid, Shaanxi workers ^ The percentage of ethylene Thallium, clavulanic acid anion, etc. As for the thickness of the injection layer, including bell ions, nano ions, gardenia, and tetradrine gardenia, such as $ nanometer to 5. nanometer. The material which is better than 2 meters can be considered in view of the "selection" between the electrode and the adjacent layers of materials. For example, it is a conductive polymer such as polyaniline, polythiophene and its derivatives, polypyridine and pyrrole, and He Biology, Poly (phenylene vinylene) and its derivatives, special _ ^ ((thienyl vinylene) and its derivatives, polyquinoline and its derivatives, polybenzyl and its derivatives, the main chain Or branched bonds containing the aromatic amine structure, such as the main image of your um, as well as metal phthalocyanine (copper phthalocyanine, etc.), carbon, etc. The insulating layer with a thickness of 2 nanometers or less has an easy charge. Injection function. As for the aforementioned insulating layer material, gold can be cited Fluoride, metal oxide, organic insulating material, etc. As for the polymer LED having an insulating layer with a thickness of 2 nanometers or less, it is worth mentioning that the polymer having an insulating layer with a thickness of 2 nanometers or less is disposed at the adjacent cathode. And polymer LEDs having an insulating layer 2 nm or less in thickness adjacent to the anode. The following structures q) to ab) are specifically cited. q) Anode / Insulating layer / Lighting layer / Cathode 2 nm or less r) Anode / Lighting layer / Insulating layer / Cathode 2 thickness or less s) Anode / Insulating layer 2 nm or less / Light-emitting layer / Insulation layer / cathode / thickness below 2) t) Anode / insulation layer / hole transmission layer / light-emitting household with thickness ^^ m or below 25 313883 (Please read the precautions on the back before filling (This page)-. _; Line _

586332 A7 B7 V. Description of the invention (26 / Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Cathodic Economy) Anode / hole transmission layer / light-emitting layer / insulation layer / cathode 2 nm or less v) Anode / thickness 2 nano M or less insulation layer / hole transport layer / light emitting layer / insulation layer 2 nm or less / cathode w) anode / insulation layer 2 thickness or less / light emitting layer / electron transport layer / cathode X) Anode / Light-emitting layer / Electronic transport layer / Insulation layer 2 nm or less / Cathode y) Anode / Insulation layer 2 nm or less / Light-emitting layer / Electron transport layer / Insulation layer 2 nm or less / Cathode z) anode / insulation layer 2 nm or less / hole transport layer / light-emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light-emitting layer / electron transport layer / thickness 2 nm or Insulation layer / cathode below ab) Anode / insulation layer 2nm or less / hole transport layer / light-emitting layer / electron transport layer / insulation layer / cathode 2nm or less When a thin film is formed by using such a solution of a polymerizable fluorescent substance which is soluble in an organic solvent, it is only necessary to borrow the solution after the solution is applied. The solvent was removed dry; even when the charge transport material is mixed with a light emitting material, the same method can still be applied to obtain a great advantage in manufacturing. As for the method for forming a thin film from a solution, a coating method such as a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a rod coating method, a roll coating method, a wire rod coating method, a dip coating method, Spraying method, screen printing method, flexographic printing method, and lithographic printing paper sizes are applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) C3271 26 313883 (Please read the precautions on the back before filling this page)

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586332 A7 V. Description of the invention (27 brush method, inkjet printing method, etc.) As for the thickness of the light-emitting layer, the optimal thickness varies depending on the materials used. The driving voltage and light-emitting efficiency can be optimally selected by appropriate selection, such as 1 nanometer to 1 micrometer, preferably 2 nanometers to 500 nanometers, and even more preferably 5 nanometers to 200 nanometers. In the polymer LED of the present invention, light emitting materials other than the aforementioned polymerized fluorescent substance may be mixed in Light-emitting layer. In addition, the light-emitting layer containing a light-emitting material other than the polymerized fluorescent substance in the polymer leD of the present invention may be laminated with the light-emitting layer containing the foregoing polymer-fluorescent substance. As the light-emitting material, known materials may be used In lower molecular weight compounds 'can use, for example, naphthalene derivatives, anthracene or its derivatives, perylene or derivatives; dyes such as polymethylol dyes, xanthene dyes, coumarin dyes' cyanine dyes 8-hydroxyquinoline or a derivative thereof, an aromatic amine, tetraphenylcyclopentane or a derivative thereof, or a metal complex of tetraphenylbutadiene or a derivative thereof, etc. In particular, known compounds such as jp_A Nos. 57-5 1 78 1, 59_ 1 95393, etc. When the polymer LED of the present invention has a hole-transporting layer, the hole-transporting material used is, for example, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a branched chain, or a main chain. Aromatic amine-containing polysiloxane derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenylenediamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof Materials, polypyrrole or its derivatives, poly (p-phenylene vinylene) or its derivatives, poly (2,5-thienyl vinylene) or its derivatives, etc. The Chinese paper standard ( CNS) A4 specification ⑵G X 297 public) 313883 (Please read the precautions on the back before filling this page) I ------ Order ---------

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 586332 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs V. Invention Description (28 Special examples of hole transmission materials include JP_A Nos. 63-70257, 63-l75860, 2-135359, 2135361 , 2-209988, 3-37992, and 3 152184. Among them, as a hole transporting material for a hole transporting layer, a polymer hole transporting material such as polyethylene or a derivative thereof is preferred. , Polylithium oxalate or its derivative, polysiloxane derivative with branched or main chain having an aromatic amine compound group, polyaniline or its derivative, polythiophene or its derivative, poly (p-phenylene) Vinyl) or a derivative thereof, poly (2,5-thienyl vinylene) or a derivative thereof; more preferably, for example, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, and branched chain Or a polysiloxane derivative containing an aromatic amine compound in the main chain. When the hole transport material has a relatively low molecular weight, it is preferably dispersed in a polymer binder for use. Cationic polymerization Or obtained by free radical polymerization. As for polysilane or its derivatives, for example, the comprehensive description of chemistry, Ying, (1989) and GB 23 00196 published in the description of the compound, etc. For the synthesis can use the methods described in these documents, especially suitable for use Kaiping method. As for the polysilicon oxygen institute or its derivatives, compounds that can be used in the structure of the aforementioned hole-transport materials with branch or primary bonds having lower molecular weights are not suitable for the hole-transport properties of the siloxane skeleton structure. Especially, compounds containing aromatic amines with branched or main chains that have hole-transport properties. — There is no particular limitation on the method for forming the hole-transport layer. When the hole-transport layer is smaller than μm, a polymer polymer surface can be used. For use by taxis and Nissei _ rulers, the national and national standard adhesives are mixed by u ^ ^ 7 X ^ 28 313883 (Please read the precautions on the back before filling out this page) • Bird — — — — — — — · 11111111

586332 V. Description of the invention (29); Method for forming a hole transport layer by valley liquid. In the case of eight or sigma hole transport materials, for example, a method of forming a hole transport layer from a solution can be used. There are no particular restrictions on the solvents used to form thin plutonium from solutions, and to dissolve hole transport materials. As for the solvent, for example, & μ ^ For example, lice solvents such as aerobic, digas, and :: dichloroethane, etc., solvents such as tetrahydrofuran, etc., aromatic hydrocarbon solvents! Solvents such as propylene residue, isobutyl acetate, etc., and vinegar solvents ^ such as ethyl acetate, butyl acetate, ethylcellosolve acetate, etc. As for the method of forming a thin film from a solution, a solution coating method 7 such as a spin coating method, a wash casting method, a micro gravure coating method, a gravure coating method, a rod coating method, a roll coating method, a wire rod coating method, Dip coating method, spraying method, screen printing method, flexographic printing method, lithographic printing method, inkjet printing method, and the like. The mixed polymer binder is preferably one that does not extremely interfere with the transport of electric charges, and is suitable for use with a polymer binder that does not have strong absorption of visible light. As for such polymer adhesives, such as polycarbonate, polyacrylic acid methyl acrylate, poly (methyl methacrylate), polystyrene, poly (gas, polysiloxane), etc. Employees of the Intellectual Property Office, Ministry of Economic Affairs Consumption cooperatives print the thickness of the hole transmission layer. The optimal value is due to the different thicknesses of the materials used. The driving voltage and luminous efficiency can be optimally selected. 'At least it needs to have no pinhole thickness.' The thickness is too large and Poor results in an increase in the driving power of the device. Therefore, the thickness of the hole transmission layer is, for example, nanometer to 1 micron, preferably 2 nanometers to 500 nanometers, and more preferably 5 nanometers to 200 nanometers. When the polymer LED of the present invention has an electron-transporting layer, it is known that the compound-the system is used as an electron-transporting material ', such as stilbazole derivatives, anthracene xylene, and paper. Applicable paper size: Zhongguanjia Standard (CNS) A4 specification ⑵Q χ 297 public love) _ 032715 29 313883 586332 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (30 alkane or its derivative, benzoquinone or its derivative, naphthoquinone or its derivative , Anthracene or its derivative, tetracyanoanthraquinone dimethane or its derivative, amidine derivative, diphenyl dicyanoethylene or its derivative, dibenzoquinone or its derivative, or 8_quinquinine or Metal complexes of its derivatives, polyquinoline and its derivatives, polyarsenoline and its derivatives, poly% or its derivatives, etc. Particularly, for example]?-Humans> 108.63-70257, 63 -175860 '2_ 135359, 2-135361, 2-209988, 3-37992, and 3-152184. Among them are panazolium derivatives, benzoquinone or its derivatives, anthraquinone or its derivatives, or 8 _Hydroxyquinoline or its derivative, polyoxoline and its derivative, polyquinoline and its derivative, polyfluorene or its metal complex is preferred; and 2- (4-linked Benzene) 5- (4-Third-butylphenyl) -1,3, rendiazole, benzothracene, anthraquinone, ginseno (8-quinolinolyl) aluminum and polyquinoline are more preferred. The method of the electron transport layer is not particularly limited. When the material has a low molecular weight, for example, a method of forming a film from a gas phase of a powder == a solution or a melted state can be used. An example of a polymer electron transport material is a solution from a solution. A method for forming a thin film in a molten state. The solvent used to form a thin film from a solution is not particularly limited, but can dissolve hole-transporting materials and / or polymer adhesives. As for the solvent, for example, a gaseous solvent such as aerosol and digas Krypton, dioxetane, etc., called aromatic solvents such as tetrazolidine, such as toluene, xylene, etc., solvents such as acetone, isobutyl ether, etc., and vinegar solvents such as ethyl acetate, butyl acetate, ethyl Fibrinolysin acetate, etc .__ As for the method of forming a thin film from a solution or a molten state, a coating side M-scale scale can be used + National National Standard (CNS) A4 specification (210 X 297 public love)-" 7C32716 30 313883 ^ --------- U (Please read the precautions on the back before filling this page)

586332

Consumers' cooperation of Intellectual Property Bureau of the Ministry of Economic Affairs Du printed: cold for example spin coating method, wash casting method, gravure coating method, gravure coating method, rod, method, roll coating method, wire rod coating method, dip coating method , Spray method, screen printing method, human printing method, f printing method, inkjet printing method, etc. The polymer binder to be mixed is preferably a polymer binder that does not extremely interfere with charge transport, and is suitable for using a T compound binder that does not strongly absorb visible light. As for such polymer adhesives, for example-mention is made of (N vinyl yesterdayazole), polyaniline or its derivatives, polythiophene or its derivatives, poly (p-phenylene vinylene) or its derivatives, Poly (2,5-thiophene-vinyl) or its derivatives, polycarbonate, polyacrylate, poly (methyl acryl), poly (methacrylase), polystyrene, Poly (gas vinyl), polysiloxane, etc. Regarding the thickness of the electron transport layer, the optimal value is due to the different thicknesses of the materials used. The driving voltage and luminous efficiency can be optimally selected. At least the thickness of the pinhole is not required. The thickness is too large, which causes the device to drive. The voltage rises. Therefore, the thickness of the hole transport layer is, for example, 1 nanometer to 1 micrometer, preferably 2 nanometers to 500 nanometers, and more preferably 5 nanometers to 200 nanometers. The polymer LED-forming substrate of the present invention is preferably a substrate that does not change when the electrodes and the organic material layer are formed, such as glass, plastic, polymer film, silicon substrate, and the like. For opaque substrates, the counter electrode is preferably transparent or translucent. In the present invention, it is preferred that the anode is transparent or translucent. As for such an anode material, a conductive metal oxide film, a translucent metal film, or the like can be used. Special use of indium oxide, oxide, tin oxide, and through the use of indium, tin, non-, and tensile scales are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) C3 ° 7i ^ 31 313883 (Please read first (Notes on the back then fill out this page) --line

586332 A7 B7 V. Description of the invention (32 Printed oxides (IT0), oxides, etc. (which are metal oxide complexes), and gold #silver, steel, etc. by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The thin film (NESA, etc.) made of conductive glass is composed of I TO, indium, zinc, and oxide tin oxide. As the argon k method, vacuum vapor deposition method, sputtering method, ion implantation method, Implantation method, etc. The anode can also use organic transparent conductive films such as polyaniline or its derivatives, polythiophene or its derivatives, etc. The thickness of the anode is appropriately selected, taking into account the light transmission and conductivity, for example, the thickness is 10 nm To 10 micrometers, preferably 20 nanometers to 1 micrometer and more preferably 50 nanometers to 500 nanometers. In addition, in order to easily inject a charge, a layer of a conductive polymer including phthaloline 2 derivative, carbon, etc. may be provided on the anode. Layer, or a layer with an average film thickness of 2 nm or less, which includes metal oxides, metal fluorides, organic insulating materials, etc. As for the cathode material used in the polymer LED of the present invention, it has a lower power Material of function is better . For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, gill, barium, aluminum, sharp, vanadium, yttrium, indium, scandium, scandium, scandium, scandium, scandium, scandium, etc .; or An alloy containing two or more of them; or one or more of gold and silver, platinum, steel, manganese, titanium, cobalt, nickel, tungsten and tin, graphite or graphite intercalation compounds, etc. Gold alloys include, for example, magnesium-silver alloys, magnesium-indium alloys, magnesium_aluminum alloys, indium_silver sigma gold, lithium · ming alloys, lithium_town alloys, lithium_indium alloys, calcium · ming alloys, etc. The cathode may be Formed as a multilayer structure of two or more layers. The thickness of the cathode is appropriately selected, taking into account light transmittance and electrical conductivity. If the thickness is 10 nm to 10 μm, preferably 20 nm to 1 μm and Benz Zhang Standards are applicable to China National Standard (CNS) A4 specifications (21〇X 297 public love) "-32 313883 (Please read the precautions on the back before filling this page) >0:; line

586332 A7 B7 Printed by the Consumer Affairs Cooperatives of the Intellectual Property Agency of the Ministry of Economic Affairs. 5. Description of the invention (33) Better 50 nm to 500 nm. As for the manufacturing method of the cathode, a vacuum vapor deposition method, a sputtering method, a lamination method can be used, in which a metal thin film is adhered under heat and pressure. In addition, 'a layer containing a conductive polymer, or an average thickness of 2 nm or less, can be provided between the cathode and the organic layer, and the layer contains metal oxides, metal fluorides, organic insulating materials, etc .; after the cathode is manufactured, it can also be A protective layer is provided to protect the polymer LED. For long-term stable use of the polymer LED ', it is preferable to provide a protective layer and / or a protective cover to protect the device from external damage. As for the protective layer, a polymer compound, a metal oxide, a metal fluoride, a metal borate, or the like can be used. As for the protective cover, a glass plate or a plastic plate may be used and the surface thereof has been subjected to low water permeability treatment. A method is suitable in which the protective cover is adhered to the device substrate by using a thermosetting resin or a light-hardening resin for sealing. If a spacer is used to maintain the space, it is easy to prevent the device from being damaged. If the internal gas such as nitrogen and argon is sealed in this space, the cathode can be prevented from being oxidized. Further, by placing a desiccant such as barium oxide in this space, it is convenient to prevent the device from being damaged by moisture adhesion during the manufacturing process. Among them, any one or more means is preferably used. In order to obtain a planar light emission using the polymer LED of the present invention, it is suitable to place a planar anode and a cathode and laminate them with each other. In order to obtain luminescence in the form of a pattern, one method is a method in which a mask having a window in the form of a pattern is placed on the aforementioned planar light-emitting device; and a method in which the organic layer of the non-light-emitting portion is formed to a great thickness to provide a method that is substantially non-luminous ; And a method in which either the anode or the cathode, or both, form a pattern. By borrowing this paper size 1¾¾ Towel® g standard (CNS) A4 specification (210 x 297 public love) " ------ C327 33 313883 (Please read the precautions on the back before filling this page) > 0 ·

586332 V. Description of the invention (34) Any method of forming a pattern and placing independent electrodes so that independent switches can be obtained. 'Segment-type display device, which can display numbers, (Please read the note on the back? Matters before Fill out this page) letters, simple symbols, etc. In addition, a dot-matrix device is constructed for τ, and the anode and cathode are preferably formed into strips, which are placed at right angles to each other. By using the following method: ¾: In this method, a plurality of polymer glory materials that emit light of different colors are separately placed, or a method in which a ocher plate or a light-emitting conversion filter is used, can obtain an area color display and a colorful display. The dot matrix display device can be driven by driving, or it can be driven by a combination of active driving and TFT. These display devices can be used as displays for computers, televisions, portable terminals, portable telephones, car navigation, visual field finders of video cameras, and the like. Further, the aforementioned planar light-emitting device is a self-light-emitting device, and is suitable for use as a planar light source for a backlight of a liquid crystal display or a planar light source for illumination. In addition, if a flexible board is used, it can also be used as a curved light source or display. [Examples] The following examples further illustrate the details of the present invention without limiting its scope. Printed by the Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs. Here, the weight average molecular weight and number average molecular weight, polystyrene equivalent molecular weight is obtained by gel permeation chromatography (GPC) using aerosol as a solvent. Example 1 0.77 g of 9,9-dioctyl-2,7-dibromofluorene, 2,5_fluorene {2,-{4 ',-(] ^, -diphenylamino) phenyl} ethylene Based} -1,4-dibromobenzene 0.05 mg, 2,2, -bispyridine 0.026 g, anhydrous vaporized nickel 0.0217 g, triphenylphosphine 0.5 g and zinc This paper applies Chinese national standards ( CNS) A4 specification (210 X 297 mm) '34 34313883 G32720 586332 A7-^^ __ Β7 ___- ^ V. Description of the invention (35) '8 grams of powder feed into the brigade. The reactor atmosphere was then flushed with argon. To this was added 8 'ml of N, N, dimethylformamide (DMF) degassed by argon beforehand. … Then the combined solution was reacted at 80 ° C for 25 hours. The reaction was performed under an argon atmosphere. Anti-employee, you cool the solution and pour it into methanol. Secondly, the income obtained by Shen Jue was retired. ,, +, Eight This gel is dried and then dissolved in aerosol. The solution was filtered to remove non-glutenous materials. The solution was poured into methanol and the resulting precipitate was collected. The precipitate was dried under reduced pressure to obtain 00 g of a polymer. The polymer is called a polymeric fluorescent substance1. The average molecular weight of the polystyrene converted number of the poly-millifluorene 1 fluorescent substance 1 was 5x103. A] blade ... The monomer feed ratio, the formula of polymerized fluorescent substance 1 and formula (8) are repeated. The unit ratio is 95: 5, and the polymerized fluorescent substance 1 is a random copolymer. (Please read the Zhuyin on the back? Matters before filling out this page)

Q Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 0

b This paper size: China National Standard (CNS) A4 specification (210 X 297 public love) 35 313883 586332 A7 ---- B7 Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Printed by Consumer Cooperatives V. Invention Description (36) Will be 9,9 -Dioctyl-2,7 · dibromonu 548 g, 2,-{4,-(N, N-diphenylamino)} phenyl-1,4-digasbenzene 0.39 g, 2, 0.624 g of 2, -bispyridine and 0.866 g of 1,5-cyclooctadiene were fed into the reactor, and then the reaction system atmosphere was flushed with argon. 20 ml of N, N'-dimethyl T-amine (DMF) which had been degassed by argon beforehand was added thereto. Then, 10 g of (1,5-cyclooctadiene) nickel (0) and 10 g were added to the mixed solution, and reacted at 7CTC for 20 hours. The reaction was performed in an argon atmosphere. After the reaction, the solution was cooled and poured into 25 ml of methanol / 50 ml of ion-exchanged water (which contained 10 liters of 25/0 nitrogen water in a mixed solvent. Next, the resulting precipitate was collected by filtration. Shen Dian was dehydrated and then dissolved in aerosol The solution was filtered to remove insoluble matter, and the solvent was collected under reduced pressure to collect the resulting sink. Shen Dian washed with C-net and dried under reduced pressure to obtain a polymer of 0.15 g. This polymer is called polymeric fluorescent substance 2. Polymerized fluorescent substance 2 的 取 # Reward 4 4 The average molecular weight of the polybenzyl ethylene equivalent molecular weight is 1.2 × 104. From the monomer feed ratio, the polymerized fluorescent substance is temporarily 9) Repeat the pre-element ratio of 50:50 with formula (10), and the polymerized fluorescent substance λ is not a good candidate for Chiyu Substance 2 is a random copolymer. (Please read the note on the back? Matters before filling out this page)

I · I.; Line

36 313883 G32722 586332 Α7 Β7 V. Description of the invention (37 Example printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 3 will be 9,9_dioctyl-2,7-dibromofluorene 0.079 g, 2- {2, _ {4 ,, _ (N, N_diphenylamino) phenyl} vinyl} -1,4_dibromobenzene 0.081 g, 2,2, _bis-pyridine 0.558 g, 1,5-cyclooctadiene 0. 432 g was fed into the reactor, and then the reaction system was flushed with argon. 20 ml of N, N'-dimethylformamide (DMF) degassed by argon beforehand was added thereto. Then 96 (1,5-cyclooctadiene) nickel (0) 0.96 g was added to the mixed solution, and the reaction was carried out at 70 ° C for 16 hours. The reaction was performed in an argon atmosphere. After the reaction, the solution was cooled and poured into methanol 25 Ml / ion-exchanged water in 50 ml (containing 10 ml of 25% ammonia) in a mixed solvent. Secondly, the resulting precipitate was collected by filtration. ^ The precipitate was dehydrated and then dissolved in aerosol. The solution was filtered to remove insoluble materials, and under reduced pressure The solvent was removed and the resulting precipitate was collected. The precipitate was washed with acetone and dried under reduced pressure to obtain a polymer of 0.5 g. This polymer was called polymeric fluorescent substance 3. The average molecular weight of the polystyrene converted number of the fluorescent substance 3 is 7 · 7χ 103. From the monomer feed ratio, the repeating unit ratio of the formula (11) and the formula (12) of the polymerized fluorescent substance 3 is 90 · 10 ′ polymerization. Fluorescent Substance 3 is a random copolymer. This paper has been scaled to the size of China National Takarazuka Standard (UNS) A4 (210 X 297 mm) C32723 37 313883 (Please read the note on the back? Matters before filling out this page) Line · 586332 Α7 Β7

V. Description of the invention (38)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (12) Example 4 Will be 9,9-one-octyl-2,7-fluorene (ethylene dihydroxyethyl borate) 0.305 g (0.575 mmol) Ear), 2] 2, {4 '(N counts diphenylamino) phenyl} vinyl oxide 1,309-dibromobenzene 0.0309 g (0.547 mol) and Aliquat 336 (230 Mg, 0.57 mmol) was dissolved in toluene (10 ml), and 10 ml of an aqueous potassium carbonate solution (240 mg, 1.7 mg) was added thereto. Add triphenylphosphine (1.3 mg, o.ooii mol) and heat to reflux for 10 hours. The organic layer was added dropwise to methanol, and the deposited sediment was collected by filtration. The obtained precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after deposition was filtered to obtain 0.25 g of polymer. This polymer is called a polymeric fluorescent substance4. The average molecular weight of the polystyrene converted number of the polymer fluorescent substance 4 was 1.8x104. From the monomer feed ratio, the repeating unit ratio of formula (13) and formula (14) of the polymerized fluorescent substance 4 is 50:50, and the polymerized fluorescent substance 4 is an alternating copolymer. This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) C32724 38 313883 (Please read the phonetic on the back? Matters before filling out this page) Order: 586332

V. Description of Invention (39

(13) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (14) Example 5 Will be 9,9-dioctyl 芴 _2,7- 贰 (ethyl dihydroxyethyl borate) 0 309 g (0.582 Millimoles), 9,9-dioctyl_2,7 · dibromo 0.274 g (0.499 millimoles), 2- {2, _ {4 ,,-(muqin diphenylamino) phenyl} Vinyl} 0.028 g (0.554 mmol) of 1,4-dibromobenzene and Alexandra 336 (230 mg, 0.57 mmol) were dissolved in toluene (10 ml), and 1Q ml of a carbonic acid oblique aqueous solution ( 240 mg, 17 mmol). Further, (triphenylphosphine) palladium (1.3 mg, 0.0001 mmol) was added, and the mixture was heated under reflux for 10 hours. The organic layer was added dropwise to methanol, and the deposited precipitate was collected by filtration. The obtained precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after deposition was filtered to obtain 0.34 g of the named polymer. This polymer is called polymeric fluorescent substance 5. The polystyrene reduced number average molecular weight of the polymerized fluorescent substance 5 was 4 × 04. The ratio of repeating units of formula (15) and formula (16) from monomer feed ratio 'polymerized fluorescent substance 5 is 95: 5, and the polymerized fluorescent substance 5 is composed of repeating units of formula (15) and (16) Random copolymer. It is inevitable that the repeating unit of formula (15) is immediately adjacent to the repeating unit of formula (16). The paper size of the table applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 39 313883 (Please read the note on the back? Matters before filling out this page) 586332 A7 i. Description of the invention (40

CaH, 7 C8H17 (15)

Q

(16) (Please read the note on the back? Matters before filling out this page) C327C6 printed by the Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs, F 6 Example 9,9 · Dioctyl 芴 _2,7- 贰Dihydroxyethyl borate) 0.305 g (0.576 millimoles), 99-dioctyl-2 sense dibromofluorene 271 g (0.494 millimoles), 2,5 Ethylcarbazolyl))-1,4-Diphenylbenzene 0.037 g (0.055 mmol) and Alkwa 336 (23 mg, 0 mmol) were dissolved in toluene (10 Ml), 10 ml of potassium carbonate aqueous solution (240 mg '1.7 mmol) was added thereto. Add palladium (triphenylphosphine) (13 mg '0: 0011 mmol) and heat to reflux for 10 hours. The organic layer was added dropwise to methanol, and the accumulated precipitate was collected by filtration. The obtained precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after deposition was filtered to obtain polymer 0 32 2. This polymer is called polymeric fluorescent substance 6. The polystyrene-equivalent average molecular weight of the polymerized fluorescent substance 6 was 3 ΐχ 104. From the monomer feed ratio, the formula (17) of polymerized fluorescent substance 6 is repeated with formula ⑽, the ratio is 95: 5, and the polymerized fluorescent substance 6 is composed of formula (17) and formula ⑽—I complex unit. Random copolymer. The standard of this paper ^ applies to Chinese national standards (CN "ΧQ Χ 297 public formula (1 7) heavy # 313883 A7 B7 V. Description of the invention (41) The unit exists next to the repeating unit of formula (18)

c8h17 c8h 17 (17)

(18) (Please read the note on the back? Matters before filling out this page) The paper printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, China Standard (CNS) A4 (21. X 297 mm) 41 Examples Put 9,9-dioctylfluorene-2,7 · fluorene (ethylene dihydroxyethyl borate) 0.305 g (0.576 mmol), 2,5-dai {2 '-{ 4 "-(] ^-diphenylamino) phenyl} vinyl} · 1,4-dibromobenzene 0.424 g (0548 mmol) and Alcoa 336 (230 mg, 0 · 57 millimoles) was dissolved in toluene (10 milliliters), and 10 milliliters of potassium carbonate aqueous solution (240 milligrams, 1.7 millimoles) was added thereto. Further, triphenylphosphine palladium (1.3 milligrams, 0 · 00ηmmol), heated to reflux for 10 hours. The organic layer was added dropwise to methanol, and the deposited precipitate was collected by filtration. The known precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after deposition; 0 14 g. This polymer is called polymerized fluorescent substance 7 ° polymerized fluorescent substance 7 has a polystyrene equivalent number average molecular weight of 8 · 8 × 10 4 〇 monomer feed ratio, polymerized fluorescent substance 7 ^ (70 ^ 9 in use Traditional Chinese opera / ηντη, Λ > 1 la Xfr / rin. Nrw ϋ 1, 1 ___ 313883 586332 A7 V. Description of the invention (42) The complex unit ratio is 50: 50, and the polymer fluorescent substance 7 is an alternating copolymer

c8h17 c8h17 (19)

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5: n ~ 〇 (20) (Please read the note on the back? Matters before filling out this page) Order-· Comparative Example will be 9,9_dioctyl 芴 -2,7- 贰Borate) 0.305 g (0.574 mmol), 9,9-dioctyl_2,7_dibromofluorene 0.300 g (0.547 mmol), and Alcoa 336 (230 mg, 0.57 mmol) Mol) was dissolved in toluene (10 ml), and 10 ml of an aqueous potassium carbonate solution (240 mg, i 7 mmol) was added thereto. Add palladium (triphenylphosphine) palladium (13 mg, 0.0011 mmol) and heat to reflux for 10 hours. The organic layer was added dropwise to methanol, and the deposited Shen Dian was collected by tritium. The obtained precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after deposition was filtered to obtain 0.38 g of polymer. This polymer is called polymeric fluorescein substance8. The polystyrene reduced number of the polymerized fluorescent substance 8 had an average molecular weight of 6.9 x 104. The polymerized fluorescent substance 8 is a polymer consisting of a repeating unit of formula (21). The paper ruler is based on the CNS A4 specification. χ 297 public love) '--- 313883-line

Printed by Consumers and Consumers' Association of Intellectual Property Bureau, Ministry of Economic Affairs 42 586332 A7

V. Description of the invention (43 jO ^ Ok CeHi7 c8h17 (21) Comparative Example 2 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 2, 9, 9-dioctyl-2,7-dioxine 548 grams, 2.benzene Group) ν (3 · xylyl)} amino-1,4 · digas benzene 0.328 g, 2,2, _ succinyl 624 g 'i, 5-cyclooctane dilute 0.866 g feed The reaction vessel, then the reaction system atmosphere was flushed with nitrogen. 20 ml of N, N'-dimethylformamide (DMF) previously degassed by argon was added thereto. Then (1,5-cyclooctadiene) nickel (0) ^ 0 g was added to the mixed solution, and the reaction was performed at m: 20 hours. The reaction was performed under an argon atmosphere. After the reaction, the solution was cooled and poured into a mixed solvent of 25 ml of methanol / ml of ion-exchanged water (containing 10 ml of 25% ammonia water). The resulting precipitate was collected by filtration. Shen Dian was dehydrated and then dissolved in aerosol. The solution was filtered to remove insoluble matter 'and then the solvent was removed under reduced pressure to collect the resulting precipitate. The precipitate was washed with acetone and dehydrated under reduced pressure to obtain 0.10 g of a polymer. This poly figure is called a polymeric fluorescent substance 9. The number of polystyrene folds of the polymerized fluorescent substance 9 was 6.8 × 103. The repeating unit ratio of formula (22) and formula (23) of polymerized fluorescent substance 9 from monomer feed ratio 'is 50:50'. Polymerized fluorescent substance 9 is a random copolymer. (Please read the precautions on the back before filling out this page) The paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) G32729 43 313883 586332 A7 ___ B7 V. Description of the invention (44)

(twenty two)

(23) Comparative Example 3 printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 9,9-Dioctyl 芴 _2,7- 贰 (Ethyl Dihydroxy — ~ 0.305 g (0.575 mmol), N, N_: (4-benzylphenyl) _N • aniline 0.221 g (0.548 mmol) and Alcoa 33 (5 (22 mg, 0.55 mmol)) dissolved in toluene (10 ml), 10 ml of carbonic acid A potassium aqueous solution (2 38 mg, 1 J mmol) was added thereto. Then (triphenylphosphine) palladium (0.3 mg, 0.0011 mmol) was added and heated under reflux for 10 hours. The organic layer was added dropwise to methanol, The deposited precipitate was collected by filtration. The resulting precipitate was dissolved in toluene and added dropwise to methanol. The precipitate after filtration was filtered to obtain a polymer of 021 g. This polyfluorene was used as a polymeric fluorescent substance H). The number average molecular weight of the polystyrene material of the polymerized glory flQ was 3.7 × 104. From the monomer feed, the formula (24) and formula (25) of polymerized glory 1G have an early ratio of 50:50 'and the polymerized fluorescent substance 10 is an alternating copolymer. Ethyl maleate) (Please read the note on the back? Matters before filling out this page) J ^ T · -line

^ SJTiiiiiMCNS) A4 specification "X 297 mm) 44 313883 586332 A7 B7 V. Description of the invention (45

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (25) Example ίο Polymerized fluorescent substances 1-10 are soluble in solvents such as toluene and aerosol. < Evaluation of fluorescent properties> A 4% by weight chloroform solution containing the polymerized fluorescent substance 1 was spin-coated on a quartz plate to form a thin film of the polymerized fluorescent substance 1. An ultraviolet-visible absorption spectrophotometer (UV 3500, manufactured by Hitachi) and a fluorescent spectrophotometer (850 manufactured by Hitachi) were used to measure the ultraviolet-visible absorption spectrum and fluorescence spectrum of the film, respectively. It is used to calculate the fluorescence intensity, and it is used for the fluorescence spectrum of 35nm nanometer excitation. The relative value of fluorescence intensity is calculated by dividing the area of the fluorescence spectrum plotted against the wave number on the horizontal axis by the absorbance at 350 nm. In the same manner as described above, fluorescence spectra of the polymerized fluorescent substances 2 to 10 in a thin film state were obtained. The polymerized fluorescent substances 1 to 10 have fluorescent peak wavelengths shown in Table 1. The polymerized fluorescent substances 1 to 8 and 10 each have strong fluorescence in the visible light region in a thin film state, but the fluorescence of the polymerized fluorescent substance 9 is extremely weak. National Paper Standard (CNS) A4 (210: 297 mm) 45 313883 (Please read the note on the back? Matters before filling out this page) M. Order --------- line "

586332 Α7 Β7 V. Description of the invention (46) Table Fluorescence characteristics of polymerized fluorescent substance

Comparative Example Polymerized Fluorescent Substance 10 436 2.42 (Please read the note on the back? Matters before filling out this page) π Example 11 < Manufacturing and Evaluation of Devices > It has been prepared with a thickness of 15 nm by the sputtering method 〇 On the glass substrate of the film, a poly (n-phenylene dioxythiophene) / polybenzene sulfonic acid solution (Baytron, manufactured by Bayer) was used to form a 50 nm thick film by spin coating. The film was 12 ° C was dried on a hot plate for 10 minutes. Next, the polymerized fluorescent substance j was spin-coated with a 15 wt% toluene solution to form a film having a thickness of about 70 nm. Further, this film was dried at 80 ° C under reduced pressure. Working hours, and then vapor-deposit 0.4 nm of lithium fluoride as the cathode buffer layer, vapor-deposit 25 nm of calcium and vapor-deposit 40 nm of aluminum as the cathode to make polymer LEDs. In any vapor deposition, vacuum Degrees are 1 to 8χ Γ (Γό Torr. This paper size applies to Chinese National Standard (CNS) A4 ¥ Grid (210 X 297 Public Welfare " 7 Ο 〇 ^ 屋 313883 line)

Printing of clothing by employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 ^ 32 586332 A7

5. Description of the invention (47) A voltage is applied to the obtained device to obtain light from the polymerized fluorescent substance iiELS. EL luminous intensity is approximately proportional to the current density. In the same way, a manufacturing apparatus using a polymerized glory substance 6 丨 8 is used. EL light emission was obtained from the polymerized fluorescent substances 6 and 8 by applying a voltage to the obtained device. The luminous intensity is almost proportional to the current density. The obtained device characteristics are shown in Table 2. Compared with the polymerized fluorescent substance 8 of Comparative Example 丨, the polymerized fluorescent substance 1 of Example 1 and the polymerized fluorescent substance 6 of Example 6 have higher luminous efficiency and maximum brightness, and also have the same or lighter light-emitting starting voltage . Although the polymerized fluorescent substance 8 of Comparative Example 1 and the polymerized fluorescent substance 10 of Comparative Example 3 had strong fluorescence (Table 1), when the device was used, the luminous efficiency was low and the brightness was also low. (Please read the precautions on the back before filling out this page) _ Printed by Employee Consumer Cooperatives, Bureau of Intellectual Property, Ministry of Economic Affairs, Table 2 Features of devices using polymerized fluorescent substances Luminous efficiency (turbidity / amp) Luminous starting voltage (volts) Max. Brightness (candle / square meter) Polymer fluorescent substance 1 0.89 3.5 3517 Polymer fluorescent substance 7 0.48 4.6 4426 Polymer fluorescent substance 8 0.09 4.6 749 Polymer fluorescent substance 10 0.08 6.0 1041 line

Example 12 0.45-g of 2,5- (2,7-dimethyl-octyloxy) -154-dibromobenzene, 2_ {4,-(N, N-diphenylamino)} phenyl_1, 0.29 g of 4-diphenylbenzene and 0.6! G of 2,2'-bipyridine were fed into the reactor, and then the reaction system atmosphere was flushed with argon. In its China National Standard (CNS) A4 specification (210 X 297 public reply) 313883 586332 A7 B7 V. Description of the invention (48 Add 50 ml of tetrahydrosangane (dehydration) by degassing by flushing. Then 贰 (1 1.2 g of 5-cyclooctadiene) nickel (〇) was added to the mixed solution, and reacted at 60 ° C for 7 hours. The reaction was performed under an argon atmosphere. After the reaction, the solution was cooled and poured into 100 ml of methanol / 100 ml of ion-exchanged water in a mixed solvent. Next, the resulting precipitate was filtered and collected. The precipitate was dehydrated and then dissolved in toluene. The solution was filtered to remove insoluble materials, purified by a silica gel feed column, and then decompressed. The solvent was removed and the resulting precipitate was collected. The precipitate was washed with ethanol and dried under reduced pressure to obtain 0.05 g of a polymer. This polymer is called polymeric fluorescent substance 11. The average molecular weight of polystyrene converted number of polymeric fluorescent substance 11 was 2 · 1χ 1104. From the monomer feed ratio, the repeating unit ratio of formula (26) and formula (27) of the polymerized fluorescent substance 11 is 50:50, and the polymerized fluorescent substance 11 is a random copolymer. Γ4 First read the (Please fill in this page again) :

(26)-Line

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

Q

: Ν-0 (27) 0.41-g 2,5- (2,7-dimethyl_octyloxy) · 1,4-dibromobenzene, 2_ {Ν- (3-methylbenzyl) aniline} 0.24 g of -1,4-digasbenzene, 0.68 of 2,2, -bispyridine should be placed in a container, but jl: the reaction system atmosphere is flushed with argon. It uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm) " " " 48 313883 586332 A7

5. Description of the invention (49) Add 50 ml of tetrahydrofuran (dehydrated) by degassing with argon beforehand. Then (1,5-cyclooctadiene) nickel (0) !. 2 g was added to the mixed solution and reacted at 60 ° C for 7 hours. The reaction was performed under an argon atmosphere. After the reaction, the solution was cooled and poured into a mixed solvent of 100 ml of methanol / 100 ml of ion-exchanged water. The resulting precipitate was then collected by filtration. The precipitate was dried and then dissolved in toluene. The solution was filtered to remove insoluble matter, purified through a silica gel feed column, and then the solvent was removed under reduced pressure to collect the service hall. The precipitate was washed with ethanol and dried under reduced pressure to obtain 0.05 g of a polymer. This polymer is called a polymeric fluorescent substance 12. The polystyrene reduced number average molecular weight of the polymerized fluorescent substance 12 was 66x103. From the monomer feed ratio, the repeating unit ratio of the formula (28) to the formula (29) of the polymerized fluorescent substance 12 is 50:50, and the polymerized fluorescent substance 12 is a random copolymer. (Please read the notes on the back before filling this page)

(28)-Line

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (29) Example 13 In the same manner as in Example 10, the fluorescence spectra of the polymerized phosphorescent substances 11 and 12 in the thin film state were obtained. _Qinhe Fluorescent Substance 11 has a thin film state in the visible light region! Xin China National Standard (CNS) A4 specification (210 X 297 mm) u32? 3o > 49 313883 586332 A7 B7 V. Description of the invention (50) Light 'but the fluorescence of polymerized fluorescent substance 12 is higher than that of polymerized fluorescent substance ^ Weak Table 3 _ Fluorescent Properties of Polymeric Fluorescent Substance 2 The substitution of fluorene is based on the branched chain, and when used in the polymer I light layer, it displays high brightness and high luminous efficiency. Therefore, polymer LEDs are better used in devices, for light sources with flat or illuminated surfaces, or as liquid crystal display stomach, segment-type displays, and dot-matrix flat-panel display lights. $ (Please read the precautions on the back before filling in this page} Fluorescent peak wavelength 424 42? Fluorescence intensity (arbitrary unit) Τη 0.46 Example 12 Comparative Example 4-Line_

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

313883 50

Claims (1)

586332 No. 91 1 16442 Patent Application Amendment to Patent Scope (December 12, 1992) 1. A polymerization that fluoresces in a solid state and has a polystyrene equivalent number average molecular weight 101 2 3 4 5 6 to 107 Fluorescent substance, the substance contains one or more repeating units represented by formula (1) and one or more repeating units represented by formula (3), -Ar] · (1) where AΓ] represents an aryl group or a divalent group Heterocyclic compound group having 1 to 4 substituents represented by the following formula (2): k 313883 (4) 1 2 where is a divalent hydrocarbon group; Ar2 represents an aryl group or a divalent heterocyclic compound group; Ar3 represents an aryl group or a monovalent heterocyclic compound group; Al 2 and Ar3 may be bonded to each other to form one Ring; Ar4 represents an aryl group or a monovalent heterocyclic compound 4 group; Aι · 3 and Aγ4 may be connected to each other to form a ring; k is 0 or 1; 5 1 represents an integer of 1 to 3, 6 -Ar5- (3) 7 wherein Ar5 represents an arylene group or a divalent heterocyclic compound group represented by formula (4) or (5): wherein χ2 represents a group selected from the group consisting of 0, s, s0, s02, NR3, CH, and SiH ; R3 to I each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic compound group; each of R and & each independently represent an alkyl group, an alkoxy group, an alkylthio group, Alkylsilyl, alkylamino, aryl, aryloxy, arylsilyl, arylamine, arylalkyl, arylalkoxy, arylalkylsilyl, arylalkylamino , Aryl alkenyl, aryl fastyl, monovalent heterocyclic compound groups, and cyano groups; m and η are each independently an integer of 0 to 3; when ^ is 2 or more days 'Multiple R] may be the same or different; when η is 2 or more, multiple R2 may be the same or different; R] may be linked to form a ring; beware that R.7 is a group containing an alkyl chain In the case of alkyl groups, the alkyl chain may be interrupted by a heteroatom-containing group. ((^) Where r8 represents a group selected from alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, and aromatic. Aryl, aryloxy, arylsilyl, arylamino, arylalkyl, arylalkoxy, arylalkylsilyl, arylalkylamino, square alkenyl, arylalkynyl , A valence heterocyclic compound group, and a cyano group, j is an integer of 0 to 3; when j is 2 or more, multiple may be the same or different; 畲 Rs is a group containing a sulphur group In this case, the alkyl chain may be interrupted by a heteroatom-containing group. For example, a polymerized fluorescent substance according to the scope of the patent application], wherein the repeating unit of formula (3) is a repeating unit represented by formula (6): 3) 3883 .: ¾ Wherein Rn and R] are each independently selected from the group consisting of a hydrogen atom, an alkyl group, an aryl group, and a monovalent heterocyclic compound group; 1 and Riq are each independently selected from an alkyl group, an alkoxy group, and an alkane group; Thio, alkylsilyl, alkylamino, square, aryloxy, arylsilyl, arylamino, arylalkyl, arylalkoxy, arylalkylsilyl, arylalkane Groups of aminoamino, arylalkenyl, arylalkynyl, monovalent heterocyclic compound, and cyano; h and 1 are each independently an integer of 0 to 3; when ^ is 2 or more , Multiple & may be the same or different; when i is 2 or more, multiple R1Gs may be the same or different; I to R] 2 may be connected to form a ring; beware to R] 2 is an alkyl chain In the case of a radical, the alkyl chain may be interrupted by a heteroatom-containing group. 3. If the polymerized fluorescent substance of item 1 of the patent application scope is based on all repeating units, the total amount of repeating units represented by formulas (1) and (3) is 50/0 mole ratio or more, and The total amount of repeating units represented by the formulas (1) and (3) is a reference. The total amount of repeating units represented by the formula (1) is 0.1% or more to 50% or more. 4. A polymer light-emitting device comprising a pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or translucent, and at least one light-emitting layer interposed between the two electrodes, wherein the light-emitting layer includes a patent application A polymeric fluorescent substance according to any one of the items 1 to 3. 313883 5 · The polymer light-emitting device according to item 4 of the patent application, wherein the layer containing a conductive polymer is arranged at least between an electrode and the light-emitting layer, so that the layer containing the conductive polymer is adjacent to the electrode. 6. The polymer light-emitting device according to item 4 of the patent application, wherein an insulating layer having a thickness of 2 nm or less is provided between at least one electrode and the light-emitting layer so that the insulating layer is adjacent to the electrode. 7. The polymer light emitting device according to any one of claims 4 to 6 of the patent application, wherein a layer containing an electron transfer compound is disposed between the cathode and. In the light-emitting layer, the layer containing the electron-transporting compound is adjacent to the light-emitting layer. 8. If any of the patent application scope items 4 to 6-Huan polymer light-emitting device, a layer containing a hole-passing compound is disposed between the anode and a 4A light layer, so that the layer containing a hole-transporting compound Adjacent to the light emitting layer. If you apply for a polymer light-emitting device of any of items 4 to 6 in the patent, the layer of Ganzhong ___ ^ AI 3 electron transfer compound is set between the cathode and the light-emitting layer, you / 7 people $ The layer basis of the electron-transporting compound is adjacent to the layer containing the hole-transporting compound, which is disposed between the anode and the light emitting corpse, /, θ $ 'so that the layer containing the hole-transporting compound is adjacent to the light-emitting layer. 1 0 · The polymer light-emitting device as in any one of the items 4 to 6 of the scope of the patent application, which is used for the flat light source 1 1 · The unit is used in the section 4 to 6 as the scope of the patent application. Any one of the polymer light-emitting display. 4 313883 586332 dZ 12. .... ... h '.;-.. ~ 一.' One, produce one .V ... · ,,,, 12 · For example, the polymer light-emitting device of any one of the range of patent application items 4 to 6 is used for a dot matrix display. 1 3 · The polymer light-emitting device of any one of the range of patent application items 4 to 6 is used Used as a backlight for the LCD monitor.